CN1185990A - Dispersing method and dispersing apparatus using supercritical state - Google Patents
Dispersing method and dispersing apparatus using supercritical state Download PDFInfo
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- CN1185990A CN1185990A CN97113670A CN97113670A CN1185990A CN 1185990 A CN1185990 A CN 1185990A CN 97113670 A CN97113670 A CN 97113670A CN 97113670 A CN97113670 A CN 97113670A CN 1185990 A CN1185990 A CN 1185990A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/30—Mixing gases with solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/50—Mixing liquids with solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/50—Mixing liquids with solids
- B01F23/51—Methods thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/50—Mixing liquids with solids
- B01F23/55—Mixing liquids with solids the mixture being submitted to electrical, sonic or similar energy
- B01F23/551—Mixing liquids with solids the mixture being submitted to electrical, sonic or similar energy using vibrations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/50—Mixing liquids with solids
- B01F23/59—Mixing systems, i.e. flow charts or diagrams
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/04—Specific aggregation state of one or more of the phases to be mixed
- B01F23/043—Mixing fluids or with fluids in a supercritical state, in supercritical conditions or variable density fluids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/20—Jet mixers, i.e. mixers using high-speed fluid streams
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F31/00—Mixers with shaking, oscillating, or vibrating mechanisms
- B01F31/80—Mixing by means of high-frequency vibrations above one kHz, e.g. ultrasonic vibrations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/45—Magnetic mixers; Mixers with magnetically driven stirrers
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Abstract
A dispersion method for uniformly dispersing solid or liquid fine particles in a solvent utilizes a supercritical fluid. A dispersoid of a solid, a liquid or the like is mixed with a solvent, and the resulting mixture is fed to a supercritical vessel. A supercritical solvent is then fed to the supercritical vessel and heated and compressed to a level higher than the critical temperature and critical pressure thereof to convert it to a supercritical fluid. The supercritical fluid and mixture of dispersoid and solvent are mixed together to form a supercritical mixture, which is released to atmospheric pressure in an explosion-crashing tank and subjected to collision within the explosion-crashing tank to efficiently disperse the dispersoid in the solvent.
Description
The solid-liquid that the present invention relates to solid (particulate) and liquid mixing dispersion is that the liquid of dispersion, liquid and liquid mixing and emulsifying and so on-liquid system disperses or solid-liquid (water)-liquid (organic solvent) is the method for dispersion, is specifically related to use the supercritical solvent of supercriticality to disperse as process for dispersing and the dispersal device of dispersion means for its feature.
In order to disperse as coating, printing ink, pottery, cosmetics, food and consolidating of other raw material is decentralized medium, has adopted kneading machine, roller mill, medium dispersion machine etc.; For the decentralized medium of emulsion system has then adopted homogenizer etc., such processing method generally needs use the regular hour owing to be to make its micronize with shearing force for dispersed particle with mechanical means, and also need carry out troublesome work such as decontaminating apparatus after processing.
In order to improve above-mentioned process for dispersing; such process for dispersing had been proposed; promptly under supercriticality, solvent is mixed with decentralized medium; by this solvent rapid expansion is allowed after the decentralized medium micronize; jet in the medium of compositions such as varnish, toluene; but in this method, particulate can take place to condense in being blown into medium the time again and might make the dispersity deterioration.
The object of the present invention is to provide the such process for dispersing and the dispersal device that utilize supercriticality, they utilize the shooting flow physical efficiency under the condition that changes pressure and temperature etc., make density become the character of liquid density continuously and promptly from gasiform density; The present invention also aims to obtain preferably can be by the process for dispersing that utilizes supercriticality and the dispersal device of computer-controlled operation.
To achieve these goals, according to the present invention, process for dispersing that utilizes supercriticality and device thereof are provided: will mix the mixture that decentralized medium becomes with solvent and be supplied in overcritical container with following characteristics, in this overcritical container, supply with supercritical solvent, this supercritical solvent of heating pressurization makes it change to supercritical fluid from gas phase state, in this overcritical container, mix aforementioned mixture and aforementioned supercritical fluid, supercritical mixtures with said mixture and supercritical fluid imports cracking groove then, in this cracking groove, spray and can bump, and above-mentioned decentralized medium is disperseed in solvent to change of atmospheric pressure.
In the present invention, so-called supercritical solvent is meant to forming the used solvent of supercriticality; And so-called supercriticality, supercritical fluid, be meant the sort of supercriticality, supercritical fluid when surpassing critical-temperature, critical pressure, though comprise it being to be lower than the sort of critical-temperature, critical pressure slightly in addition, but because the state variation of phase transformation can take place in the extremely short time, thereby subcritical state, the subcritical fluids that can handle by the mode of basically identical with above-mentioned supercriticality, supercritical fluid.
So-called quick-fried broken among the present invention is meant the operation that can produce following effect.
(1) when decentralized medium is the porous particle, in its pore or fine gap, because the immersion of supercritical fluid, when rapid decompression, under the rapid volumetric expansion effect, can produce the effect of fragmentation, dispersion;
(2) from the shower nozzle of slit dispersion liquid, to ultrasonic flow velocity ejection, produce fragmentation, dispersion effect with high detrusion effect for decentralized medium with velocity of sound with supercriticality with pore or close clearance;
(3) under corresponding to the inertia force effect of quality of ejection liquid particle with collision such as wall, can give decentralized medium therefrom with percussion, produce broken, dispersion effect.
Fig. 1 is the key diagram of process for dispersing for solid (particulate)-liquid of the present invention, wherein (A) for the operation of packing into of slip, (B) be supercriticality chemical industry preface, (C) when stirring for adopting jet flow to mix operation, (D) be the quick-fried broken nozzle of employing with vertical tabular impact portions the time quick-fried broken operation.
Fig. 2 is the key diagram of agitating device, and wherein (A) shows that jet flow stirs, (B) shows that ultrasonic wave stirs, (C) shows that the oscillating plate, (D) that are driven by outside shifting magnetic field show the revolution wing that is driven by outside shifting magnetic field.
Fig. 3 shows the impact portions of bright cracking groove, (A), (B) all be the key diagram when having adopted the impingement plate of band cover, (C) is the key diagram of convection current crash scenario.
Fig. 4 shows under room temperature, normal pressure the temperature and the operating process of pressure that forms supercriticality from the gas supercritical solvent, and wherein (A) be that temperature and pressure operating process, (B) are that expression, (C) of temperature and pressure operating process in density-pressure thermoisopleth is the curve map that shows temperature and pressure operating process representation in density-temperature isobaric chart.
Fig. 5 shows under room temperature, normal pressure the temperature and the operating process of pressure that forms supercriticality from the liquid supercritical solvent, and wherein (A) be that temperature and pressure operating process, (B) are that expression, (C) of temperature and pressure operating process in density-pressure isollaothermic chart is the curve map that shows temperature and pressure operating process representation in density-temperature isobaric chart.
Fig. 6 shows the process for dispersing of liquid of the present invention-liquid system, and (A) pack into key diagram, the key diagram that mixes operation, (D) when (B) stirs for adopting jet flow for the key diagram of supercriticality chemical industry preface, (C) of emulsion operation of explanation is the key diagram of quick-fried broken operation when having adopted quick-fried broken nozzle with vertical tabular impact portions.
Fig. 7 illustrates dispersal device one embodiment of the present invention.
The embodiment that Fig. 8 explanation disperses according to the present invention and the dispersity of comparative example.
Fig. 9 is the curve map that shows that the particle diameter of the embodiment that disperses according to the present invention and comparative example distributes.
The principle of process for dispersing of the present invention is described with reference to the accompanying drawings.The decentralized medium that Fig. 1 shows is the solid system particulate and it is distributed to situation in the liquid system solvent.The solid system particulate here for example is the ultra micron of pigment, ceramic powder, magnetic particle etc., also includes several particulates sometimes; The solvent of liquid system then is included in the dispersion liquid water that forms continuous phase, organic solvent etc., and the two mixture (hereinafter referred to as slip) under suspended state (rough segmentation is loose) is supplied to (Fig. 1 (A)) in this container from the supply port 30 of overcritical container 6.At this moment, preferably add dispersant such as macromolecule interfacial activating agent and other suitable reagent in advance.In this stage, solia particle a ... the generally most particulate of formation, even the aggregation of particle is the state of aggregation of so-called particle, and they are present in the suspended state in solvent.
According to the character of dispersant, also above-mentioned slip can be supplied in aforementioned container after pre-dispersed device is pre-dispersed, or directly be supplied in this container without premixed.
The supply port nozzle 8 of supercritical solvent from overcritical container 6 is filled in this container.For forming supercritical fluid, above-mentioned supercritical solvent is reached on critical-temperature, the critical pressure, heating such as the pump of setting up on the used said vesse, heater pressue device is to this supercritical solvent heating, pressurization (Fig. 1 (B)).The supercritical fluid b that makes like this ... compare with liquid fluxs such as water or ethanol, diffusion coefficient strengthens and surface tension reduces, thereby soaks particulate easily, can infiltrate particulate a apace ... aggregation in.Because the interaction (gravitation) of particulate and supercritical fluid is greater than constituting the interaction (gravitation) between each particulate in the above-mentioned aggregation, then particle aggregate just size degradation become one by one particle, carry out granulation one time, promoted the dispersion of particulate.At this moment, when having pore c in the above-mentioned particulate, as mentioned above, because this supercritical fluid has big diffusion coefficient and little surface tension, just shown in the enlarged drawing among Fig. 1, supercritical fluid promptly soaks in the pore c that is contained in particulate a.
For further strengthening between an above-mentioned granulation or particulate or in its pore soaking of supercritical fluid contained, can stir the supercritical mixtures (Fig. 1 (c)) of above-mentioned slip and supercritical fluid in the overcritical container with agitating device.Diversified stirring means can be arranged, but preferably adopt shaft etc. not run through the closed structure of overcritical container.As Fig. 1 and shown in Figure 2, in the overcritical container of subtend nozzle 8 is set, by pump P4 the circulation port 31 that forms in the overcritical container 6 is connected with nozzle 8, pump is to aforementioned supercritical mixtures circulation pressurization thus, make it be ejected in the overcritical container and in container, produce circular flow and mix, promote to homogenize from nozzle 8.
Agitating device shown in Fig. 2 (B) is that ultrasonic wave is transmitted in the overcritical container 6, and the mixture in the stirred vessel and make its homogenizing has omitted therewith on the container set ultrasonic wave and injected the ultrasonic generator that hole 32 is connected among the figure.
Solenoid also can be set to be made outside overcritical container 6 and to produce the shifting magnetic field and come mixture in the stirred vessel.In the embodiment shown in Fig. 2 (C), in container, be provided with the vibration generation body 34 of the band oscillating plate 33 that vibrates by outside shifting magnetic field, drive vibration via the solenoid 35 that produces outside shifting magnetic field bodies 34 take place, make oscillating plate 33 vibrations and stir.
In Fig. 2 (D) illustrated embodiment, in overcritical container, be provided with rotor 37, it has and can act on the revolution wing 36 that rotates down in revolution shifting magnetic field externally, drive such rotation body 37 via the solenoid 38 that produces the revolution shifting magnetic field, the revolution wing 36 is rotated stir.
As mentioned above, discharge from the flow export 39 of overcritical container 6 through the supercritical mixtures that all agitating devices mix, the pipeline 9 that joins by flow export 39 therewith imports cracking grooves 10, the warp-wise atmospheric pressure discharges and sprays in this cracking groove 10, promotes the form of disperseing impacting impact portions (Fig. 1 (D)) to produce percussion.The ejiction opening 12 of this cracking groove 10 can be the quick-fried broken nozzle 40 (Fig. 3 (A)) that has the pore of suitable internal diameter or have slit, or having the quick-fried broken window 41 (Fig. 3 (B)) of suitable aperture area, 9 of the pipelines that this quick-fried broken nozzle etc. is connected with the flow export 39 of overcritical container 6 are preferably heated by set heater (not showing bright).
As aforesaid impact portions, shown in Fig. 3 (A), 3 (B), formed the place aheads such as surrounding said nozzle, window and below open impingement plate 13, this has formed the vertical vertical plate 13a of emission direction of relative nozzle 40 under the situation of nozzle 40; And under the situation of quick-fried broken window 41, then forming hemispherical plate 13b with respect to this quick-fried broken window 41, feasible dispersion liquid by ejections such as said nozzles can generally perpendicularly collide wall, gives effective impulsive force.
Above-mentioned impact portions also can not adopt plate-like piece.At this moment, also can be shown in Fig. 3 (c), with the state in the subtend cracking groove 10 quick-fried broken nozzle 40,40 is set, pipeline 9 forks from overcritical container 6, connect quick- fried yawper 40,40 respectively, and the dispersion liquid of each nozzle 40,40 is sprayed relative to each other, these two strands of dispersion liquids are run foul of each other, the impact during by collision promotes to disperse.In addition, quick-fried broken nozzle 40,40 can be arranged in the cover 42 in the cracking groove 10, and the dispersion liquid that makes the nozzle ejection is not below dispersing towards periphery after the collision mutually and flowing to.
As mentioned above; in cracking groove 10; the volume of the supercritical solvent in the above-mentioned particle aggregate sharply expands; thereby make this aggregation can further make its each particle become the state of a granulation; at this moment; when particulate has pore, owing to soak the volumetric expansion that is contained in supercritical solvent in the pore, particulate itself will further be pulverized, disperse.
In above-mentioned technical process, form heating, pressurized operation that supercritical fluid carries out for making supercritical solvent, preferably can become supercriticality mutually from gas phase state as described below.Fig. 4 shows and understands and to be used at the temperature that makes gas when supercritical solvent is formed into supercriticality under room temperature, the normal pressure and the operation change procedure of pressure, wherein (A) shows the operation change procedure of temperature and pressure, (B) is temperature and pressure operating process showing in density-pressure isollaothermic chart; (C) be the expression of temperature and pressure operating process in density-temperature isobaric chart, the heavy line among the figure is represented each operating process.
Among the last figure, in the operating process (1) of process path sequence number 1 → 2 → 5 expressions, path 1 → 2 expression is from the gas fluidify, and path 2 → 5 expressions are changed to supercritical fluid from liquid.When this observed concerning that phase and solids disperse, because the particle surface during by the vapor liquid equilibrium district is that liquid soaks, after this, supercritical fluid just was difficult within the immersion areola etc.The result, supercritical solvent soaks between the crack that is contained in the solids aggregate or just mainly is to be undertaken by the molecular diffusion in the organic solvent equal solvent in the slip in the pore of solids, even arrived supercriticality, the influence that also becomes supercritical fluid is difficult to feed through between the crack of solids aggregation or the state in the pore in the solids.So, just become inadequate state in an aforesaid granulation of being undertaken by dispersion in the supercriticality or quick-fried broken effect.
In the operation in path 1 → 3 → 5, on path 1 → 3, only gas is compressed shown in the operating process (2); On path 3 → 5, gas promptly becomes supercritical fluid continuously.At this moment, owing to be to be transformed to supercritical fluid continuously, so the shooting flow physical efficiency is soaked in the pore of the gap that is contained in the solids aggregation or solids well from gas.
In the operation in the path 1 → 4 → 5 shown in the operating process (3), on path 1 → 4, only carry out the gas compression; On path 4 → 5, gas becomes supercritical fluid continuously.At this moment, identical with aforesaid operations process (2), the soaking of supercritical fluid contains good, by computer factors such as controlled pressure, temperature, density effectively, can select solids disperse in good state, can in the short time, carry out scatter operation.For the control that disperses in the solid-liquid system, for example can become to soak easily making the density low-densityization of supercritical fluid at first contains, and pressurization after this makes its densification, improves wetting quality, releases to atmospheric pressure in cracking groove then.
Under normal temperature, normal pressure, make operating process that liquid forms supercriticality from supercritical solvent as shown in Figure 5.Identical with Fig. 4, (A) is the temperature and pressure operation among Fig. 5, and (B) expression of temperature and pressure operating process in density-pressure isollaothermic chart (C) is expression in the density-temperature isobaric chart of temperature and pressure operating process.The operating process of this moment can at first make temperature be raised to more than the critical-temperature shown in path 1 → 2 → 3 or 1 → 4 → 3, is gas from liquid phase-change, adds then to press to supercritical fluid.At this moment, though above-mentioned fluid has passed through gas-liquid phase transition, this becomes the little phase transformation of density mutually, can think to enter in the solids pore or solids aggregation gap in not influence of impregnability.
As mentioned above, make supercritical solvent become supercriticality and have all operating process, wherein, through associate gas to the phase transformation of liquid be that density becomes big phase transformation, through the liquid of associating to the phase transformation that diminishes for density of the phase transformation of gas, in the phase transformation that density diminishes, can not hinder supercritical fluid to soak to be contained in solids to focus in the pore of the gap of body or particle, in the present invention, in order to become supercritical fluid through gas phase state, operation heating pressue device.
Fig. 6 shows and bright the liquid system decentralized medium is distributed to drop process for dispersing in the solution.At this, the dispersion solute of liquid system such as fat globule, suspend (rough segmentation is loose) among water, organic solvent equal solvent,, so that being mixture (hereinafter referred to as emulsion), all liquid-liquid of multiple organic solute-organic solvent system or the like joins in the overcritical container 6 (Fig. 6 (A)) as two kinds in water-organic solvent system, organic solute-organic solvent system etc. from supply port 30.At this moment preferably add additives such as dispersant, reagent in advance.
In overcritical container 6, mix (Fig. 6 (c)) by agitating device then.In this figure, show bright be by pump P4 with supercritical mixtures circulation, pressurization, and be ejected into the device that waits in the said vesse, but also can adopt all devices shown in the prior figures 2 from nozzle 8.According to this operation; in above-mentioned Fig. 6 (B) under the state shown in (1) figure, drop is to carry out micronize from sub-micron like that to micron-sized footpaths of number, and in Fig. 6 (B) situation of (2) figure; then can further promote homogenization, become better dispersity.
Above-mentioned supercritical mixtures through mixing from the flow export 39 guiding cracking grooves 10 of overcritical container 6, is ejected into (Fig. 6 (D)) in this groove from the ejiction opening 12 of the quick-fried broken nozzle of this cracking groove 10 or quick-fried broken window etc.At this moment, state shown in (1) figure among Fig. 6 (B), the volume of supercritical solvent sharply expands in the drop, the drop miniaturization, disperse the dispersion of solute, or shown in (2) figure among Fig. 6 (B),,, the dispersion liquid of uniform state drips the dispersion liquid in good condition that exists with atomic little dispersion solute just becoming in liquid because supercritical solvent evaporates sharp, disperses.Again because above-mentioned dispersion liquid to being located in the cracking groove 10 the rapid percussion of impact portions as shown in Figure 3, just can further promote dispersion.Above-mentioned each operation can be by computer control, and operational example is at this moment released to atmospheric pressure in cracking groove then as can fully dissolving in disperseing solute making supercritical fluid be in high-density state at first.
Generally show decentralized system optimum device one embodiment that implements above-mentioned process for dispersing among Fig. 7.
One as carrying out premixed embodiment as requested among Fig. 7, be provided with pre-mixing apparatus such as kneading machines such as roller mill, kneading machine 1 or planetary-type mixer 2, plant pre-mixing apparatus thus with mixing such as decentralized medium, solvent, dispersants, again the pump P1 supply dispersion sample regulating tank 3 of this mixture by snakelike pump, screw extruder etc.Preferably be provided with as shown in Figure 7 in the regulating tank 3 and be used for preventing granules precipitation, aggegation and make the mixer 4 that disperses separating of solute and solvent etc.
Groove 3 is connected with medium dispersion machine 5 by valve V1, dispersion sample liquid-feeding pump P2, and medium dispersion machine 5 is connected with the supply port 30 of overcritical container 6 by dispersion sample liquid-feeding pump P3, flowmeter M1, the valve V2 that can boost to about 200 atmospheric pressures.
Be provided with pressure gauge G, thermometer T1 in the overcritical container 6, flow export 39 is by external heater heating, and is provided with the pipeline 9 that prevented cold heater and is connected, and pipeline 9 is connected with cracking groove 10 with flow agent M3 by the pressure-reducing valve V6 that is with actuator.
Be provided with demarcation strip 11 in the cracking groove 10 up, aforementioned pipeline is connected with the ejiction opening 12 of quick-fried broken nozzle, quick-fried broken window etc., and the impingement plate 13 of band cover is then arranged in the place ahead of ejiction opening 12.The quick-fried broken nozzle here adopts as the nozzle of being made used band heater in the particulate process by supercritical fluid, stops up with anti-freeze.
The bottom of cracking groove 10 is connected with storage tank (deaeration groove) 15 by positive displacement pump P7, flowmeter M4, and storage tank 15 mixes dispersion liquid by heating mantles 16 heating of band temperature controller with mixer 17.Be provided with thermometer T2 in the storage tank 15, perhaps as required, also can the retracting device that be communicated with aforementioned dashpot 14 be set above storage tank 15, be used for reclaiming from dispersion liquid and isolate but the supercritical solvent that do not reclaim.
Aforesaid dispersion sample is regulated the outlet 18,19,20,21,22 that is respectively equipped with the band valve that is used to discharge detergent remover with groove 3, medium dispersion machine 5, overcritical container 6, cracking groove 10, storage tank 15.The temperature that records by thermometer T1, T2, the pressure that records by pressure gauge, the data on flows that records by flowmeter M1～M4, be sent to and carry out calculation process in the computer, signal is sent to the actuator of pump P1～P7, valve V1～V5, the temperature controller, the heater of pipeline 9 of heating outer cover 7,16, add heat etc. with ON/OFF, outer cover and the heater of the lifting rate of control pump respectively, valve.
The following describes the operating sequence of aforementioned system, (at solid-liquid is situation, for example is to contain ultra microns such as pigment, ceramic powder, magnetic particle, contains the situation of multiple particulate with decentralized medium.At liquid-liquid is situation, it for example is the dispersion solute of hydrophobic liquid such as fat, organic reagent, monomer etc. and the liquid of water-liquid system, or organic solvent and be not the liquid of dispersion solutes such as the fat of its dissolving, organic reagent, monomer-liquid system) place and disperse reagent regulating tank 3, as required, mixing (promotes particulate, the dispersant that disperses solute to disperse with reagent, or make microparticle surfaces have surface modifier, coating agent of all functional characteristics etc.) or water, organic solvent equal solvent, be blended into normal concentration, become aqueous dispersion liquid (slip, emulsion).In this stage, close above-mentioned valve V1, V2, V4, open above-mentioned valve V3, V5, V6.
Then, open valve V4 (shut off valve V1, V2, open valve V3, V5, V6), with carbon dioxide, ethene, substitute fluon and other supercritical solvent and send among overcritical container 6, cracking groove 10, the dashpot 14 etc., make the air of their inside of these solvent exchanges.
After replacement Treatment, close above-mentioned valve V3～V6, open valve V1, V2.To disperse the dispersion sample in the sample regulating tank 3 to give medium dispersion machine 5 with pump P2, decentralized medium and solvent or reagent etc. are mixed into more uniform state (when when disperseing sample to stir into very uniform state in regulating with groove 3, also can economize except that medium dispersion machine 5 and the washing lotion outlet 19 or valve 1, the pump 2 etc. that are attached to it), via pump 3 piezometric of regulation is gone in the overcritical container 6.
Again above-mentioned valve V1, V2 are closed, open valve V4 (valve V3, V5, V6 are in closed condition), supercritical solvent is filled in the overcritical container 6, in order to form predetermined temperature (do not damage the temperature of decentralized medium character and state and more than critical-temperature), pressure (be about critical pressure 2 times), carry out by the intensification of outer cover 7 with form supercriticality by the pressurization of pump P5.More than operation be carry out according to Fig. 4,5 illustrated be the optimum operation of object with the decentralized medium.
So far, shut off valve V4 opens valve V3.At this moment, valve V1, V2, V5, V6 are in closed condition, and overcritical container 6 becomes and outside isolated state, will be jetted from nozzle 8 by the dispersion sample of pump P4 pressurization subsequently, by the inside that injection stream stirs overcritical container, promote to disperse.
Shut off valve V3 opens valve V6 (valve V1, V2, V4, V5 are in closed condition) then, and dispersion liquid is sprayed to cracking groove 10 via the ejiction opening 12 of quick-fried broken nozzle or quick-fried broken window etc.Dispersion liquid is because the quick-fried broken effect of the expansion of supercritical solvent and can further promote to disperse to the collision (also can adopt the convection current collision) of the impingement plate of band cover.In addition, since the facilitation effect of above-mentioned dispersion die down with the decompression of overcritical container 6.Monitor the pressure in the overcritical container 6, reach the ejection that the critical pressure degree is carried out dispersion liquid to it.
In above-mentioned cracking groove 10, the supercritical solvent separation of from dispersion liquid, gasifying.By demarcation strip 11 parts, the spittle of dispersion liquid captured in the supercritical solvent of cracking groove 10 bottoms then boosts for compression pump P6 pressurization via filter F 2, dashpot 14 in liquid form reclaim, storage, circulate as described later.
Above-mentioned dispersion liquid is transported to storage tank 15 by pump P7.Heated by outer cover 16 in storage tank 15, the supercritical solvent that evaporation, separation are not reclaimed will disperse solute to be concentrated into predetermined concentration.
Shut off valve V3, V6 open valve V1, V2, dispersion liquids such as slip, emulsifying agent are filled into carry out next one circulation in the container 6.In the above-mentioned supercritical solvent of filling, valve V1, V2, V3, V4, V6 are in closed condition, and valve V5 then opens, and bring into use the supercritical solvent in the dashpot 14, and shut off valve V5 opens valve V4 and replenishes inadequate supercritical solvent then.
Embodiment
With the carbon dioxide is supercritical solvent, and (ケ Star チ ェ Application Black International corporate system, carbon ECP) places pure water to carry out distributed test with carbon black, makes following Sample A-D.
Sample A-in pure water, add the above-mentioned carbon black of 2% (weight), after having carried out being equivalent to the following operation of operating process among Fig. 4 (3), carry out quick-fried broken again:
(20 ℃, 1atm)-(5 minutes) → (20 ℃, 20atm)-(5 minutes)
→ (50 ℃, 50atm)-(5 minutes) → (60 ℃, 100atm, 5 minutes)-
(quick-fried broken) → (20 ℃, 1atm).
(above-mentioned operation letter illustrates such operation: kept 5 minutes down in 20 ℃, 1atm, kept 5 minutes down in 20 ℃, 20atm, kept 5 minutes down in 50 ℃, 50atm again, continuing kept 5 minutes under 60 ℃, 100atm, quick-friedly became 20 ℃, 1atm after broken.The identical Therefore, omited of the expression of following operational sequence).
Sample B-in pure water, add the above-mentioned carbon of 2% (weight), after having carried out being equivalent to the following operation of operating process among Fig. 4 (1), carry out quick-fried broken again:
(20 ℃, 1atm)-(7 minutes) → (20 ℃, 100atm)-(8 minutes)
→ (60 ℃, 100atm, 5 minutes) → (quick-fried broken)
Sample C-adds the dispersant of the above-mentioned carbon black and 3% (weight) of 2% (weight) in pure water, carry out 2 hours dispersion treatment with the mixer of 4 propeller wings.
Sample D-adds the above-mentioned carbon black of 2% (weight) in pure water, make 2 hours dispersion treatment with the mixer of 4 propeller wings.
The result
Said sample A～D is left standstill 100 hours relatively their differences in vitro, learn the difference indicated just like Fig. 8 key diagram.
Sample A still was even dispersion after 100 hours, become the fine dispersion state that cohesion no longer takes place.
Sample B has the cohesion again (X) of a little, and sedimentation (Y) takes place, and has part water (Z) to separate, and compares with Sample A, and dispersity is poor.
What water and carbon black took place later on from 1 hour for sample C and sample D separates the dispersity extreme difference.
When measuring sample big or small, in Sample A-B, do not find the particle of particle diameter less than 5 μ m with the particle diameter of 0～50 μ m rule (JIS-K5400).On the other hand, then have the particle of particle diameter 33 μ m among the sample C, have the particle of particle diameter 40 μ m among the sample D.
According to above result as can be known, adopt process for dispersing and the dispersal device that utilizes supercriticality of the present invention, can form good dispersity.
In addition, in order to understand fully quick-fried broken effect of the present invention, prepared sample E.
Sample E-adds the above-mentioned carbon black of 2% (weight) in pure water, after having formed supercriticality, carried out decompression (that is to say, do not carry out quick-fried broken) slowly having carried out being equivalent to the following operation of operating process among Fig. 4 (3):
(20 ℃, 1atm)-(5 minutes) → (20 ℃, 20atm)-(5 minutes)
→ (50C, 50atm)-(5 minutes) → (60 ℃, 100atm, 5 minutes) (60 minutes) → (20 ℃, 1atm)
The result
Employing is by particle size distribution analyzer (セ イ シ Application enterprise of Co., Ltd. system of light scattering method, laser miniature sizes sizing mill, the PRO-7000S type), the particle diameter of having tested carbon black in the dispersion liquid of said sample A-D and sample E distributes, obtained result shown in Fig. 9, thus the result as can be known, by quick-fried broken, Sample A, B compare with sample E and have obtained uniform particle diameter distribution, have affirmed quick-fried broken effect.
Under said structure; the present invention makes decentralized medium and solvent; again it is mixed with supercritical fluid in overcritical container; spray this supercritical mixtures by cracking groove; quick-fried broken after; in solid (particulate)-liquid is in the dispersion; (diffusion coefficient is big in low-density; viscosity is little) under the state; can enter for supercritical fluid in the pore of the gap of the aggregation of particulate or particulate itself; the pressure that then raises causes high density than (intermolecular interaction is big; wetting quality to particulate is good); can promote a granulation of particulate, and then sharply decompression (releasing to atmospheric pressure) makes density sharply reduce (volume increasing), so disperse and after dispersion, also be difficult for cohesion more effectively.In addition, in the dispersion that liquid (dispersion solute)-liquid (water) is, the solubility of utilization under high-density state is big, supercritical fluid is dissolved in the drop of the dispersion solute in the liquid (water) (under certain situation, become the homogeneous state of water-dispersion solute-supercritical fluid), sharply decompression (releasing to atmospheric pressure) makes density sharply reduce (volume increase) then, promotes to disperse, and can be difficult for producing cohesion again.Even the situation at high viscosity slip etc. also can import above-mentioned supercritical fluid viscosity is significantly reduced, thus by from ejections such as nozzles, just can be easily broken, disperse.
In addition; above-mentioned in order to promote by the dispersity of supercritical solvent to soaking in solid particle surfaces or its pore, a granulation; can control the optimum operation process of selecting temperature and pressure reliably to corresponding operating by computer; and can be when releasing promote further to disperse by the impact portions of cracking groove to atmospheric pressure; supercritical solvent can also be reclaimed circularly, thereby the decentralized system of resource-saving type can be obtained.
Claims (20)
1. utilize the process for dispersing of supercriticality, it is characterized in that: the mixture that decentralized medium becomes with solvent is supplied with overcritical container, supercritical solvent is supplied with in this overcritical container, heating pressurization makes this supercritical solvent become from gas phase state to be supercritical fluid, but said mixture supercritical fluid therewith mixes in overcritical container, supercritical mixtures with said mixture and supercritical fluid imports cracking groove then, in cracking groove, release to atmospheric pressure, bump with impact portions, disperse above-mentioned decentralized medium.
2. utilize the process for dispersing of supercriticality according to claim 1, it is characterized in that: supercritical solvent is separated with supercritical mixtures, reclaim this isolated supercritical solvent and it is supplied with overcritical container.
3. utilize the process for dispersing of supercriticality according to claim 1, it is characterized in that: the mixture of above-mentioned decentralized medium and solvent is to make the solid system decentralized medium be suspended in slip in organic solvent, the water equal solvent.
4. utilize the process for dispersing of supercriticality according to claim 1, it is characterized in that: the mixture of above-mentioned decentralized medium and solvent is to make liquid system disperse solute to be suspended in emulsion in organic solvent, the water equal solvent.
5. utilize the process for dispersing of supercriticality according to claim 1, it is characterized in that: the mixture of above-mentioned decentralized medium and solvent is to make the decentralized medium of solid system and liquid system be suspended in slip in the solvent of liquid system.
6. utilize the process for dispersing of supercriticality, it is characterized in that: supercritical fluid is imported in the mixture of decentralized medium and solvent and reduce viscosity, this low viscous mixture is under reduced pressure sprayed from pore, come fragmentation, disperse this decentralized medium for above-mentioned decentralized medium with volumetric expansion, high shear and percussion.
7. dispersal device, this dispersal device comprises: overcritical container, it has the supply unit of mixture of filling decentralized medium and solvent and the supply unit of filling supercritical solvent, also has flow export; The heating pressue device is used for the supercritical solvent in above-mentioned overcritical container heating, adds and be pressed into supercritical fluid; Agitating device is used for supercritical mixtures with said mixture and supercritical fluid in overcritical container for stirring; Cracking groove, it has ejiction opening, and be connected with the flow export of aforementioned overcritical container and described supercritical mixtures is released to atmospheric pressure, and the storage tank that is used for storing the dispersion liquid that obtains through this cracking groove.
8. as dispersal device as described in the claim 7, it is characterized in that: above-mentioned cracking groove is connected with and is used for reclaiming from the dashpot of isolated supercritical solvent wherein, and this dashpot then is connected with the supply unit of the supercritical solvent of described overcritical container.
9. as dispersal device as described in the claim 7, it is characterized in that: on the mixture supply unit of described overcritical container, be connected with and be used for the pre-mixing apparatus of aforementioned decentralized medium of premixed and solvent.
10. as dispersal device as described in the claim 7, it is characterized in that: described heating pressue device can be used to make supercritical solvent to form supercritical fluid from gas phase state.
11. as dispersal device as described in the claim 7, it is characterized in that: this agitating device comprises: the supercritical mixtures circulation that the nozzle that is provided with in the aforementioned overcritical container of subtend and making flows out from overcritical container is to the circulating pump of this nozzle.
12. as dispersal device as described in the claim 7, it is characterized in that: described agitating device includes to be located at and is used in the overcritical container to wherein launching hyperacoustic ultrasonic generator.
13. as dispersal device as described in the claim 7, it is characterized in that: described agitating device comprises: be located at the solenoid of overcritical external container and can be located at the oscillating deck or the revolution wing in this overcritical container drivingly by the shifting magnetic field that this solenoid produces.
14., it is characterized in that: be provided with the impact portions that makes the supercritical mixtures collision in the aforementioned cracking groove as dispersal device as described in the claim 7.
15. as dispersal device as described in the claim 14, it is characterized in that: the ejiction opening that is located at the supercritical mixtures in the described cracking groove is quick-fried broken nozzle, and described impact portions vertically is provided with respect to this nozzle.
16. as dispersal device as described in the claim 14, it is characterized in that: the ejiction opening that is located at the supercritical mixtures in the cracking groove is quick-fried broken window, described impact portions then with respect to this quick-fried broken window by hemispherical setting.
17. dispersal device as claimed in claim 7 is characterized in that: the ejiction opening of being located at the supercritical mixtures in the cracking groove is to make the opposite nozzles of colliding mutually between the described supercritical mixtures, constitutes impact portions and plant nozzle thus.
18. dispersal device, this dispersal device comprises: have the ejiction opening of the pore that the mixture of the decentralized medium that supercritical fluid imported and reduced viscosity and solvent under reduced pressure sprays, and be provided with and give the impact portions of decentralized medium to impact that this ejiction opening sprays.
19. as dispersal device as described in the claim 18, it is characterized in that: described impact portions is the impingement plate that is oppositely arranged with ejiction opening.
20. as dispersal device as described in the claim 18, it is characterized in that: described impact portions is to make decentralized medium make the convection current impact portions of its collision with the relative status ejection.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8358871A JPH10192670A (en) | 1996-12-27 | 1996-12-27 | Dispersion and dispersing apparatus utilizing supercritical state |
| JP358871/1996 | 1996-12-27 | ||
| JP358871/96 | 1996-12-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1185990A true CN1185990A (en) | 1998-07-01 |
| CN1057480C CN1057480C (en) | 2000-10-18 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97113670A Expired - Fee Related CN1057480C (en) | 1996-12-27 | 1997-06-24 | Dispersing method and dispersing apparatus using supercritical state |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5921478A (en) |
| EP (1) | EP0850682A1 (en) |
| JP (1) | JPH10192670A (en) |
| KR (1) | KR100283238B1 (en) |
| CN (1) | CN1057480C (en) |
| SG (1) | SG60111A1 (en) |
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- 1997-11-20 US US08/975,367 patent/US5921478A/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| US5921478A (en) | 1999-07-13 |
| KR100283238B1 (en) | 2001-04-02 |
| KR19980063361A (en) | 1998-10-07 |
| CN1057480C (en) | 2000-10-18 |
| JPH10192670A (en) | 1998-07-28 |
| SG60111A1 (en) | 1999-02-22 |
| EP0850682A1 (en) | 1998-07-01 |
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